CN110776497A - Preparation method for constructing two-dimensional organic layer based on cation-pi interaction - Google Patents
Preparation method for constructing two-dimensional organic layer based on cation-pi interaction Download PDFInfo
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- 230000003993 interaction Effects 0.000 title claims abstract description 24
- 239000012044 organic layer Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 79
- -1 (2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tris (ethane-2, 1-diyl) Chemical group 0.000 claims abstract description 73
- 239000002904 solvent Substances 0.000 claims abstract description 73
- WRNZHESDLXCFSM-UHFFFAOYSA-L dipotassium;4-(4-sulfonatophenyl)benzenesulfonate Chemical compound [K+].[K+].C1=CC(S(=O)(=O)[O-])=CC=C1C1=CC=C(S([O-])(=O)=O)C=C1 WRNZHESDLXCFSM-UHFFFAOYSA-L 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 47
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 37
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- 239000012043 crude product Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 claims description 20
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 239000012074 organic phase Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 12
- 125000000593 indol-1-yl group Chemical group [H]C1=C([H])C([H])=C2N([*])C([H])=C([H])C2=C1[H] 0.000 claims description 12
- 239000003480 eluent Substances 0.000 claims description 11
- FQWHSUNDNXZWIV-UHFFFAOYSA-N 1-(2-imidazol-1-ylethyl)indole Chemical compound C1=CC2=CC=CC=C2N1CCN1C=CN=C1 FQWHSUNDNXZWIV-UHFFFAOYSA-N 0.000 claims description 10
- ABSXMLODUTXQDJ-UHFFFAOYSA-N 4-(4-sulfophenyl)benzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1C1=CC=C(S(O)(=O)=O)C=C1 ABSXMLODUTXQDJ-UHFFFAOYSA-N 0.000 claims description 10
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000004090 dissolution Methods 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 10
- MWUVMGYIPOWLAH-UHFFFAOYSA-N 2-indol-1-ylethanol Chemical compound C1=CC=C2N(CCO)C=CC2=C1 MWUVMGYIPOWLAH-UHFFFAOYSA-N 0.000 claims description 8
- GJAKRSMIGJJOFV-UHFFFAOYSA-N 1,3,5-tris(2-bromoethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound BrCCN1C(=O)N(CCBr)C(=O)N(CCBr)C1=O GJAKRSMIGJJOFV-UHFFFAOYSA-N 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 claims description 5
- 238000004639 Schlenk technique Methods 0.000 claims description 5
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 5
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 239000012312 sodium hydride Substances 0.000 claims description 5
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 5
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 5
- KGBJBRTZJPVFAB-UHFFFAOYSA-N [Na].C1=CC(S(=O)(=O)O)=CC=C1C1=CC=C(S(O)(=O)=O)C=C1 Chemical compound [Na].C1=CC(S(=O)(=O)O)=CC=C1C1=CC=C(S(O)(=O)=O)C=C1 KGBJBRTZJPVFAB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 18
- MGMVOXYEEIGQEG-UHFFFAOYSA-L disodium;4-(4-sulfonatophenyl)benzenesulfonate Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1C1=CC=C(S([O-])(=O)=O)C=C1 MGMVOXYEEIGQEG-UHFFFAOYSA-L 0.000 abstract description 11
- 239000000178 monomer Substances 0.000 abstract description 5
- 238000010276 construction Methods 0.000 abstract description 3
- NSKLVXLAOGZGCL-UHFFFAOYSA-N [K].C1=CC(S(=O)(=O)O)=CC=C1C1=CC=C(S(O)(=O)=O)C=C1 Chemical compound [K].C1=CC(S(=O)(=O)O)=CC=C1C1=CC=C(S(O)(=O)=O)C=C1 NSKLVXLAOGZGCL-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001768 cations Chemical group 0.000 abstract description 2
- 238000005232 molecular self-assembly Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 5
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 3
- JSAMRKKTNZLLNY-UHFFFAOYSA-N 1-(2-bromoethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound BrCCN1C(=O)NC(=O)NC1=O JSAMRKKTNZLLNY-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
- C07C309/32—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings containing at least two non-condensed six-membered aromatic rings in the carbon skeleton
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention relates to a preparation method for constructing a two-dimensional organic layer based on cation-pi interaction, which obtains three required construction monomers by an organic synthesis means: 1,1', 1 "- ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tris (ethane-2, 1-diyl)) tris (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazol-3-ium) hexafluorophosphate, [1,1' -biphenyl ] -4,4' -disulfonic acid potassium and [1,1' -biphenyl ] -4,4' -disulfonic acid sodium salt. The three monomers comprise different cation units and different pi units, and can realize self-classification recognition through competition in solution, thereby allowing 1,1' - ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tris (ethane-2, 1-diyl)) tris (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazol-3-ium) hexafluorophosphate and potassium [1,1' -biphenyl ] -4,4' -disulfonate (or sodium [1,1' -biphenyl ] -4,4' -disulfonate) to efficiently undergo molecular self-assembly, by volatilizing the solvent, the supermolecule two-dimensional material 1 (or the supermolecule two-dimensional material 2) with high strength and good stability is obtained.
Description
Technical Field
The invention belongs to the field of supramolecular materials, and relates to a preparation method for constructing a two-dimensional organic layer based on cation-pi interaction.
Background
The two-dimensional material constructed based on cation-pi self-assembly is a novel supermolecule two-dimensional material, has higher stability and modifiability, and can keep good stability in various solvents, temperatures and complex mixed systems. Has great application prospect in the aspects of catalysis, conductive materials, flexible electronic materials, self-repairing materials and the like. In addition, the corresponding monomer is simple and efficient to synthesize, and can be prepared on gram-scale, so that the method has good reference value in the aspect of preparation of novel two-dimensional supramolecular materials.
Document 1 "Guanjun Chang, Li Yang, Junxiao Yang, Mark p.stoykovich, Xu Deng, Jiaxi Cui, and Dapeng wang, high-Performance pH-switched macromolecular thermoplastic resin preparation method, 30,17042, 34" discloses a preparation method of a recyclable Cation-pi crosslinked thermosetting resin, a crosslinked structure of a high-Performance polymer is obtained through Cation-pi interaction, and the requirements of people on high thermal stability and high strength of the high-Performance polymer are met, and the physical crosslinking mode can be released under the external "stimulation" condition, so that the recovery and recycling of the polymer are realized. The three-dimensional polymer constructed by the research is still irregular, and the direction of cation-pi interaction is not well regulated, so that the three-dimensional polymer is used for constructing a two-dimensional material.
Document 2, "Kang-Da Zhang, Jia Tian, David Hanifi, Yuebiao Zhang, Andrew Chi-Hau Sue, Tian-You Zhou, Lei Zhang, Xin Zhao, Yi Liu, and Zhuan-Ting Li. Toward As-Layer Two-Dimensional hierarchical Home molecular Organic Framework in Water. J.am.chem.Soc.2013,135, 17913-17918" discloses that a Two-Dimensional Supramolecular Organic Framework is constructed in an aqueous solution by host-guest interaction, and the novel Supramolecular material is simple in construction method, but the strength and stability of the Two-Dimensional material are insufficient, and the Two-Dimensional material is difficult to be applied in a solid form by being separated from the solution.
Document 3 "Bo Song, Zhijiang Wang, Senlin Chen, Xi Zhang, et al, the introduction of Pi-Pi Stacking Moieties for purifying Stable supramolecular structures: Formation and Dynamics of Disklike micelles. Angew. chem.2005,117, 4809-4813" discloses an efficient method for preparing supramolecular two-dimensional materials, but because of the construction by amphiphilic molecules, the requirements for the type of solvent are high and the selectivity of the solvent is poor.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a preparation method for constructing a two-dimensional organic layer based on cation-pi interaction, which solves the problems of poor stability of the conventional two-dimensional supramolecular material and poor regulation and control performance of the cation-pi interaction.
Technical scheme
A preparation method for constructing a two-dimensional organic layer based on cation-pi interaction is characterized by comprising the following steps:
step 1: dissolving 1,3, 5-tri (2-hydroxyethyl) triazine-2, 4, 6-trione and triphenylphosphine in a molar ratio of 1: 3.6 in anhydrous acetonitrile, and cooling in an ice bath for 5-10 minutes; adding 3.6 equivalents of carbon tetrabromide under continuous stirring, recovering to room temperature during stirring, and reacting for 10-12 hours; removing solvent under reduced pressure, dissolving the concentrated solution in appropriate amount of dichloromethane, washing with saturated sodium chloride water solution for 1-2 times, mixing organic phases, drying with anhydrous sodium sulfate, and removing solvent under reduced pressure to obtain crude product;
separating the obtained crude product with gel chromatographic column, wherein the eluent is n-hexane to obtain white crystalline solid 1,3, 5-tris (2-bromoethyl) -1,3, 5-triazacyclohexane-2, 4, 6-trione;
step 2: sequentially mixing indole, 2-bromoethanol, tetrabutylammonium iodide and potassium hydroxide according to a molar ratio of 1: 2: 0.1: 3, and adding N, N-dimethylformamide as a solvent to obtain a solution; removing oxygen from the solution by a Schlenk technology, heating to 80-90 ℃ under the protection of nitrogen atmosphere, and stirring for reacting for 20-24 hours; after the reaction is finished, cooling the reaction mixture to room temperature, removing the solvent under reduced pressure, separating the residue by using a gel chromatographic column, and obtaining light yellow liquid 2- (1H-indol-1-yl) ethyl-1-ol by using petroleum ether and ethyl acetate as eluent, wherein the ratio of the petroleum ether to the ethyl acetate is 3: 1;
and step 3: mixing the 2- (1H-indol-1-yl) ethan-1-ol and triphenylphosphine in the step 2 according to a molar ratio of 1: 1.2, and adding 100ml of acetonitrile for ice bath cooling for 5-10 minutes; adding 1.2 equivalent carbon tetrabromide under continuous stirring, stirring and slowly returning to room temperature, and reacting for 5-6 hours; removing solvent under reduced pressure, dissolving the concentrated solution in 100ml dichloromethane, washing with saturated sodium chloride water solution for 2 times, mixing organic phases, drying with anhydrous sodium sulfate, and removing solvent under reduced pressure to obtain crude product; separating the obtained crude product with gel chromatographic column, wherein the eluent is n-hexane to obtain yellow oily liquid 2- (1H-indol-1-yl) ethyl-1-bromine;
and 4, step 4: dispersing sodium hydride in an anhydrous 1, 4-dioxane solution in a Schlenk flask, and then adding imidazole into the stirred mixed solution under the protection of nitrogen; then heating the mixture to 70-85 ℃, stirring and reacting for 1.0-1.5 hours; then dropwise adding the 2- (1H-indol-1-yl) ethyl-1-bromine obtained in the step (3) into the reaction solution, and after the system is stable, heating to 100-105 ℃ and refluxing for 10-12 hours; after the reaction is finished, cooling the reaction liquid to room temperature, removing the solvent under reduced pressure, dissolving the reaction liquid in 100ml of dichloromethane again, washing the reaction liquid for 2 times by using water, combining organic phases, drying the organic phases by using anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain a crude product; separating the obtained crude product with gel chromatographic column, wherein the eluent is ethyl acetate to obtain red oily liquid 1- (2- (1H-imidazole-1-yl) ethyl) -1H-indole;
and 5: mixing the 1,3, 5-tris (2-bromoethyl) -1,3, 5-triazacyclohexane-2, 4, 6-trione obtained in the step 1 and the 1- (2- (1H-imidazol-1-yl) ethyl) -1H-indole obtained in the step 4 according to a molar ratio of 1: 4.5, adding 1, 4-dioxane as a solvent, heating to 100-105 ℃, stirring and refluxing for 20-24 hours; after the reaction is finished, cooling to room temperature, decompressing to remove the solvent, adding tetrahydrofuran, precipitating a large amount of solid, filtering, washing a filter cake for 3-4 times by using tetrahydrofuran, and drying to obtain a brown yellow solid 1,1' - ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tri (ethane-2, 1-diyl)) tri (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazole-3-onium) bromine salt;
step 6: dissolving the 1,1' - ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tri (ethane-2, 1-diyl)) tri (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazole-3-onium) bromine salt obtained in the step 5 in 50-70 mL of methanol; dropwise adding a saturated ammonium hexafluorophosphate methanol solution under stirring until the precipitate is not separated out, and continuously stirring for 30-40 minutes; filtering, washing a filter cake with methanol and water for 3-4 times respectively, and drying to obtain a yellow solid 1,1' - ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tri (ethane-2, 1-diyl)) tri (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazole-3-onium) hexafluorophosphate;
and 7: dissolving [1,1 '-biphenyl ] -4,4' -disulfonic acid and potassium hydroxide in deionized water according to a molar ratio of 1: 2, stirring the reaction solution at room temperature for 15-30 minutes, and then carrying out vacuum freeze drying to obtain white potassium [1,1 '-biphenyl ] -4,4' -disulfonate;
and 8: dissolving 1,1' - ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tri (ethane-2, 1-diyl)) tri (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazole-3-onium) hexafluorophosphate obtained in the step 6 and potassium [1,1' -biphenyl ] -4,4' -disulfonate obtained in the step 7 in a dimethyl sulfoxide solution according to a molar ratio of 3: 1, and performing ultrasonic treatment for 3 minutes to promote complete dissolution; reducing the pressure to-0.09 to-0.1 MPa, and completely removing the solvent at 90 to 95 ℃; and after the reaction is finished, cooling the obtained solid to room temperature to obtain the two-dimensional organic layer constructed based on the cation-pi interaction.
Replacing step 7 and step 8 with the following step 7a and step 8a, another two-dimensional organic layer built on the basis of cation-pi interactions was obtained:
step 7 a: dissolving [1,1 '-biphenyl ] -4,4' -disulfonic acid and sodium hydroxide in deionized water according to a molar ratio of 1: 2, stirring for 15-30 minutes at room temperature, and then carrying out vacuum freeze drying to obtain white [1,1 '-biphenyl ] -4,4' -disulfonic acid sodium;
step 8 a: dissolving 1,1' - ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tri (ethane-2, 1-diyl)) tri (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazole-3-onium) hexafluorophosphate obtained in the step 6 and [1,1' -biphenyl ] -4,4' -disulfonic acid sodium obtained in the step 7a in dimethyl sulfoxide solution according to a molar ratio of 3: 1, and performing ultrasonic treatment for 2-3 minutes to promote complete dissolution; reducing the pressure to-0.09 to-0.1 MPa, and completely removing the solvent at 90 to 95 ℃; and after the reaction is finished, cooling the obtained solid to room temperature to obtain another two-dimensional organic layer constructed based on cation-pi interaction.
The Schlenk technique is as follows: after the reactants and the solvent were added to a dried Schlenk tube, the tube was frozen with liquid nitrogen, and then, under the atmosphere of nitrogen, vacuum was applied, nitrogen was introduced, and then, liquid nitrogen was again frozen, and thus, the freezing-thawing-freezing operation was repeated several times.
The anhydrous acetonitrile is a solvent obtained after drying a 5A molecular sieve.
The 1, 4-dioxane solvent is a solvent obtained by drying a 5A molecular sieve.
All solution heating was carried out under constant temperature oil bath conditions.
The solution is cooled in an ice bath at the temperature of 0 ℃ in an ice-water mixture.
Advantageous effects
The preparation method for constructing the two-dimensional organic layer based on the cation-pi interaction obtains two new supramolecular two-dimensional materials by a mode of supramolecular self-assembly from bottom to top. First, the three building monomers required are obtained by a series of organic synthesis approaches: 1,1', 1 "- ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tris (ethane-2, 1-diyl)) tris (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazol-3-ium) hexafluorophosphate, [1,1' -biphenyl ] -4,4' -disulfonic acid potassium and [1,1' -biphenyl ] -4,4' -disulfonic acid sodium salt. The three monomers comprise different cation units and different pi units, and can realize self-classification recognition through competition in solution, thereby allowing 1,1' - ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tris (ethane-2, 1-diyl)) tris (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazol-3-ium) hexafluorophosphate and potassium [1,1' -biphenyl ] -4,4' -disulfonate (or sodium [1,1' -biphenyl ] -4,4' -disulfonate) to efficiently undergo molecular self-assembly, by volatilizing the solvent, the supermolecule two-dimensional material 1 (or the supermolecule two-dimensional material 2) with high strength and good stability is obtained. The novel two-dimensional material has a great application prospect in the aspects of catalysis, conductive materials, flexible electronic materials, self-repairing materials and the like.
Drawings
FIG. 1 is a schematic representation of the molecular structure of (2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tris (ethane-2, 1-diyl)) tris (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazol-3-ium) hexafluorophosphate prepared by the process of the present invention.
FIG. 2 is a schematic view of the molecular structure of potassium [1,1 '-biphenyl ] -4,4' -disulfonate.
FIG. 3 is a schematic diagram of the molecular structure of sodium [1,1 '-biphenyl ] -4,4' -disulfonate.
Fig. 4 is a transmission electron microscope image of the two-dimensional supramolecular organic layer prepared in example 1 of the method of the invention.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
example 1:
step 1,3, 5-tris (2-hydroxyethyl) triazine-2, 4, 6-trione (1.0g, 3.82mmol) and triphenylphosphine (3.6g,13.72mmol) were dissolved in anhydrous acetonitrile (100mL) and cooled in an ice bath for 10 min. Carbon tetrabromide (4.56g,13.72mmol) was added slowly with constant stirring. The mixture was stirred and slowly returned to room temperature, and reacted for 12 hours. Removing solvent under reduced pressure, dissolving the concentrated solution in appropriate amount of dichloromethane, washing with saturated sodium chloride water solution and water solution for 2 times, respectively, mixing organic phases, drying with anhydrous sodium sulfate, and removing solvent under reduced pressure to obtain crude product. The crude product obtained was separated by gel chromatography using n-hexane as eluent to give 1,3, 5-tris (2-bromoethyl) -1,3, 5-triazacyclohexane-2, 4, 6-trione as a white crystalline solid (yield 90%).
Step 2, indole (1.0g,8.53mmol), 2-bromoethanol (2.13g,17.1mmol), tetrabutylammonium iodide (0.31g,0.85mmol) and potassium hydroxide (1.4g,25.6mmol) were added in this order to a single-neck round-bottom flask, and 100ml of N, N-dimethylformamide was added as a solvent. The above solution was deoxygenated by Schlenk technique, after which the solution was heated to 80 ℃ under nitrogen atmosphere and the reaction was stirred for 24 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, the solvent was removed under reduced pressure, and the residue was separated on a gel chromatography column eluting with petroleum ether: ethyl acetate ═ 3: 1, light yellow liquid 2- (1H-indol-1-yl) ethan-1-ol (yield 70%) is obtained.
Step 3, 2- (1H-indol-1-yl) ethan-1-ol (2.0g,12.4mmol) and triphenylphosphine (3.9g,14.9mmol) were added sequentially to a single-neck round-bottom flask, 50ml of acetonitrile was added, and the mixture was cooled in ice bath for 10 minutes. Carbon tetrabromide (4.9g,14.9mmol) was added slowly with constant stirring. The mixture was stirred and slowly returned to room temperature, and reacted for 6 hours. Removing solvent under reduced pressure, dissolving the concentrated solution in appropriate amount of dichloromethane, washing with saturated sodium chloride water solution and water solution for 2 times, respectively, mixing organic phases, drying with anhydrous sodium sulfate, and removing solvent under reduced pressure to obtain crude product. The crude product obtained was separated by gel chromatography eluting with n-hexane to give 2- (1H-indol-1-yl) ethyl-1-bromo as a yellow oily liquid (84% yield).
Step 4, sodium hydride (64%) (0.27g,6.7mmol) was dispersed in 20ml of anhydrous 1, 4-dioxane solution in a Schlenk flask. Imidazole (0.46g,6.7mmol) was then added slowly to the stirred mixed solution under nitrogen. The mixture was then heated to 70 ℃ and the reaction stirred for 1.5 hours. Then, the 2- (1H-indol-1-yl) ethyl-1-bromine (1.0g,4.5mmol) obtained in the step 3 is slowly dripped into the reaction solution, and after the system is stable, the temperature is raised to 105 ℃ for refluxing for 12 hours. After the reaction was completed, the reaction solution was cooled to room temperature, the solvent was removed under reduced pressure, and redissolved in an appropriate amount of dichloromethane, and then washed with water for 2 times, the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to obtain a crude product. The crude product obtained was separated by gel chromatography eluting with ethyl acetate to give 1- (2- (1H-imidazol-1-yl) ethyl) -1H-indole as a red oily liquid (yield 85%).
Step 5,1, 3, 5-tris (2-bromoethyl) -1,3, 5-triazacyclohexane-2, 4, 6-trione (0.2g,0.45mmol) and 1- (2- (1H-imidazol-1-yl) ethyl) -1H-indole (0.64g,2.69mmol) were added to a single-neck flask, 25ml of 1, 4-dioxane was added as a solvent, and heating was carried out to 105 ℃ with stirring and refluxing for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, the solvent is removed under reduced pressure, tetrahydrofuran is added to precipitate a large amount of solid, the solid is filtered, a filter cake is washed for 3 times by the tetrahydrofuran and dried to obtain a brown yellow solid 1,1' - ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tri (ethane-2, 1-diyl)) tri (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazole-3-onium) bromine salt (the yield is 78%).
Step 6, 1', 1 "- ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tris (ethane-2, 1-diyl)) tris (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazol-3-ium) bromide salt was dissolved in an appropriate amount of methanol. Under the condition of continuously stirring, slowly dropwise adding saturated ammonium hexafluorophosphate methanol solution until the precipitate is not separated out, and continuously stirring for 30 minutes. The filtrate was filtered, and the filter cake was washed 3 times with methanol and water, respectively, and dried to give 1,1', 1 "- ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tris (ethane-2, 1-diyl)) tris (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazol-3-ium) hexafluorophosphate as a yellow solid (yield 90%).
Step 7, [1,1 '-biphenyl ] -4,4' -disulfonic acid (100mg,0.318mmol) and potassium hydroxide (35.7mg,0.636mmol) were dissolved in 10ml of deionized water. The reaction solution was stirred at room temperature for 30 minutes, followed by vacuum freeze-drying to obtain white potassium [1,1 '-biphenyl ] -4,4' -disulfonate (yield 99%).
Step 8, 1', 1 "- ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tris (ethane-2, 1-diyl)) tris (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazol-3-ium) hexafluorophosphate (89.5mg,0.070mmol) and potassium [1,1' -biphenyl ] -4,4' -disulfonate (8.9mg,0.023mmol) were dissolved in 3.0ml of dimethyl sulfoxide solution and sonicated for 3 minutes to facilitate complete dissolution. The pressure was reduced to-0.1 MPa, and the solvent was slowly removed at 90 ℃. And after the reaction is finished, cooling the obtained solid to room temperature to obtain the two-dimensional organic layer constructed based on the cation-pi interaction.
Example 2:
replacing steps 7 and 8 with steps 7a and 8 a:
step 7a, [1,1 '-biphenyl ] -4,4' -disulfonic acid (100mg,0.318mmol) and sodium hydroxide (25.4mg,0.636mmol) were dissolved in 10ml of deionized water. The reaction solution was stirred at room temperature for 30 minutes, followed by vacuum freeze-drying to give white sodium [1,1 '-biphenyl ] -4,4' -disulfonate (yield 99%).
Step 8a, 1', 1 "- ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tris (ethane-2, 1-diyl)) tris (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazol-3-ium) hexafluorophosphate (89.5mg,0.070mmol) and sodium [1,1' -biphenyl ] -4,4' -disulfonate (8.23mg,0.023mmol) were dissolved in 3.0ml of dimethyl sulfoxide solution and sonicated for 3 minutes to facilitate complete dissolution. The pressure was reduced to-0.1 MPa, and the solvent was slowly removed at 90 ℃. And after the reaction is finished, cooling the obtained solid 3 to room temperature to obtain another two-dimensional organic layer constructed based on cation-pi interaction.
Example 3:
step 1,3, 5-tris (2-hydroxyethyl) triazine-2, 4, 6-trione (2.0g, 7.64mmol) and triphenylphosphine (7.2g,27.48mmol) were dissolved in anhydrous acetonitrile (200mL) and cooled in an ice bath for 10 min. Carbon tetrabromide (9.12g,27.44mmol) was added slowly with constant stirring. The mixture was stirred and slowly returned to room temperature, and reacted for 12 hours. Removing solvent under reduced pressure, dissolving the concentrated solution in appropriate amount of dichloromethane, washing with saturated sodium chloride water solution and water solution for 2 times, respectively, mixing organic phases, drying with anhydrous sodium sulfate, and removing solvent under reduced pressure to obtain crude product. The crude product obtained was separated by gel chromatography using n-hexane as eluent to give 1,3, 5-tris (2-bromoethyl) -1,3, 5-triazacyclohexane-2, 4, 6-trione as a white crystalline solid (yield 90%).
Step 2, indole (2.0g,16.06mmol), 2-bromoethanol (4.26g,34.2mmol), tetrabutylammonium iodide (0.62g,1.70mmol) and potassium hydroxide (2.8g,51.2mmol) were added in this order to a single-neck round-bottom flask, and 200ml of N, N-dimethylformamide was added as a solvent. The above solution was deoxygenated by Schlenk technique, after which the solution was heated to 80 ℃ under nitrogen atmosphere and the reaction was stirred for 24 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, the solvent was removed under reduced pressure, and the residue was separated on a gel chromatography column eluting with petroleum ether: ethyl acetate ═ 3: 1, light yellow liquid 2- (1H-indol-1-yl) ethan-1-ol (yield 70%) is obtained.
Step 3, 2- (1H-indol-1-yl) ethan-1-ol (4.0g,24.8mmol) and triphenylphosphine (7.8g,29.8mmol) were added sequentially to a single-neck round-bottom flask, 100ml of acetonitrile was added, and the mixture was cooled in ice bath for 10 minutes. Carbon tetrabromide (9.8g,29.8mmol) was added slowly with constant stirring. The mixture was stirred and slowly returned to room temperature, and reacted for 6 hours. Removing solvent under reduced pressure, dissolving the concentrated solution in appropriate amount of dichloromethane, washing with saturated sodium chloride water solution and water solution for 2 times, respectively, mixing organic phases, drying with anhydrous sodium sulfate, and removing solvent under reduced pressure to obtain crude product. The crude product obtained was separated by gel chromatography eluting with n-hexane to give 2- (1H-indol-1-yl) ethyl-1-bromo as a yellow oily liquid (84% yield).
Step 4, sodium hydride (64%) (0.54g,13.4mmol) was dispersed in 40ml of anhydrous 1, 4-dioxane solution in a Schlenk flask. Imidazole (0.92g,13.4mmol) was then added slowly to the stirred mixed solution under nitrogen. The mixture was then heated to 70 ℃ and the reaction stirred for 1.5 hours. Then, the 2- (1H-indol-1-yl) ethyl-1-bromine (2.0g,9.0mmol) obtained in the step 3 is slowly dripped into the reaction solution, and after the system is stable, the temperature is raised to 105 ℃ for refluxing for 12 hours. After the reaction was completed, the reaction solution was cooled to room temperature, the solvent was removed under reduced pressure, and redissolved in an appropriate amount of dichloromethane, and then washed with water for 2 times, the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to obtain a crude product. The crude product obtained was separated by gel chromatography eluting with ethyl acetate to give 1- (2- (1H-imidazol-1-yl) ethyl) -1H-indole as a red oily liquid (yield 85%).
Step 5,1, 3, 5-tris (2-bromoethyl) -1,3, 5-triazacyclohexane-2, 4, 6-trione (0.4g,0.9mmol) and 1- (2- (1H-imidazol-1-yl) ethyl) -1H-indole (1.28g,5.38mmol) were added to a single-neck flask, 50ml of 1, 4-dioxane was added as a solvent, and heating was carried out to 105 ℃ with stirring and refluxing for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, the solvent is removed under reduced pressure, tetrahydrofuran is added to precipitate a large amount of solid, the solid is filtered, a filter cake is washed for 3 times by the tetrahydrofuran and dried to obtain a brown yellow solid 1,1' - ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tri (ethane-2, 1-diyl)) tri (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazole-3-onium) bromine salt (the yield is 78%).
Step 6, 1', 1 "- ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tris (ethane-2, 1-diyl)) tris (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazol-3-ium) bromide salt was dissolved in an appropriate amount of methanol. Under the condition of continuously stirring, slowly dropwise adding saturated ammonium hexafluorophosphate methanol solution until the precipitate is not separated out, and continuously stirring for 30 minutes. The filtrate was filtered, and the filter cake was washed 3 times with methanol and water, respectively, and dried to give 1,1', 1 "- ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tris (ethane-2, 1-diyl)) tris (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazol-3-ium) hexafluorophosphate as a yellow solid (yield 90%).
Step 7, [1,1 '-biphenyl ] -4,4' -disulfonic acid (200mg,0.636mmol) and potassium hydroxide (71.4mg,1.272mmol) were dissolved in 20ml of deionized water. The reaction solution was stirred at room temperature for 30 minutes, followed by vacuum freeze-drying to obtain white potassium [1,1 '-biphenyl ] -4,4' -disulfonate (yield 99%).
Step 8, 1', 1 "- ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tris (ethane-2, 1-diyl)) tris (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazol-3-ium) hexafluorophosphate (179.0mg,0.140mmol) and potassium [1,1' -biphenyl ] -4,4' -disulfonate (17.8mg,0.046mmol) were dissolved in 6.0ml of dimethyl sulfoxide solution and sonicated for 3 minutes to facilitate complete dissolution. The pressure was reduced to-0.1 MPa, and the solvent was slowly removed at 90 ℃. And after the reaction is finished, cooling the obtained solid to room temperature to obtain the two-dimensional organic layer constructed based on the cation-pi interaction.
Example 4:
replacing steps 7 and 8 with steps 7a and 8 a:
step 7a, [1,1 '-biphenyl ] -4,4' -disulfonic acid (200mg,0.636mmol) and sodium hydroxide (50.8mg,1.272mmol) were dissolved in 20ml of deionized water. The reaction solution was stirred at room temperature for 30 minutes, followed by vacuum freeze-drying to give white sodium [1,1 '-biphenyl ] -4,4' -disulfonate (yield 99%).
Step 8a, 1', 1 "- ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tris (ethane-2, 1-diyl)) tris (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazol-3-ium) hexafluorophosphate (179.0mg,0.140mmol) and sodium [1,1' -biphenyl ] -4,4' -disulfonate (16.46mg,0.046mmol) were dissolved in 6.0ml of dimethyl sulfoxide solution and sonicated for 3 minutes to facilitate complete dissolution. The pressure was reduced to-0.1 MPa, and the solvent was slowly removed at 90 ℃. And after the reaction is finished, cooling the obtained solid to room temperature to obtain another two-dimensional organic layer constructed based on cation-pi interaction.
Example 5:
step 1,3, 5-tris (2-hydroxyethyl) triazine-2, 4, 6-trione (3.0g, 11.46mmol) and triphenylphosphine (10.8g,41.16mmol) were dissolved in anhydrous acetonitrile (300mL) and cooled in an ice bath for 10 min. Carbon tetrabromide (13.68g,41.16mmol) was added slowly with constant stirring. The mixture was stirred and slowly returned to room temperature, and reacted for 12 hours. Removing solvent under reduced pressure, dissolving the concentrated solution in appropriate amount of dichloromethane, washing with saturated sodium chloride water solution and water solution for 2 times, respectively, mixing organic phases, drying with anhydrous sodium sulfate, and removing solvent under reduced pressure to obtain crude product. The crude product obtained was separated by gel chromatography using n-hexane as eluent to give 1,3, 5-tris (2-bromoethyl) -1,3, 5-triazacyclohexane-2, 4, 6-trione as a white crystalline solid (yield 90%).
Step 2, indole (3.0g,25.59mmol), 2-bromoethanol (6.39g,51.3mmol), tetrabutylammonium iodide (0.93g,2.55mmol) and potassium hydroxide (4.2g,76.8mmol) were added in this order to a single-neck round-bottom flask, and 300ml of N, N-dimethylformamide was added as a solvent. The above solution was deoxygenated by Schlenk technique, after which the solution was heated to 80 ℃ under nitrogen atmosphere and the reaction was stirred for 24 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, the solvent was removed under reduced pressure, and the residue was separated on a gel chromatography column eluting with petroleum ether: ethyl acetate ═ 3: 1, light yellow liquid 2- (1H-indol-1-yl) ethan-1-ol (yield 70%) is obtained.
Step 3, 2- (1H-indol-1-yl) ethan-1-ol (6.0g,37.2mmol) and triphenylphosphine (11.7g,44.7mmol) were added sequentially to a single-neck round-bottom flask, 150ml of acetonitrile was added, and the mixture was cooled in ice bath for 10 minutes. Carbon tetrabromide (14.7g,44.7mmol) was added slowly with constant stirring. The mixture was stirred and slowly returned to room temperature, and reacted for 6 hours. Removing solvent under reduced pressure, dissolving the concentrated solution in appropriate amount of dichloromethane, washing with saturated sodium chloride water solution and water solution for 2 times, respectively, mixing organic phases, drying with anhydrous sodium sulfate, and removing solvent under reduced pressure to obtain crude product. The crude product obtained was separated by gel chromatography eluting with n-hexane to give 2- (1H-indol-1-yl) ethyl-1-bromo as a yellow oily liquid (84% yield).
Step 4, sodium hydride (64%) (0.81g,20.1mmol) was dispersed in 60ml of anhydrous 1, 4-dioxane solution in a Schlenk flask. Imidazole (1.38g,20.1mmol) was then added slowly to the stirred mixed solution under nitrogen. The mixture was then heated to 70 ℃ and the reaction stirred for 1.5 hours. Then, the 2- (1H-indol-1-yl) ethyl-1-bromine (3.0g,13.5mmol) obtained in the step 3 is slowly dripped into the reaction solution, and after the system is stable, the temperature is raised to 105 ℃ for refluxing for 12 hours. After the reaction was completed, the reaction solution was cooled to room temperature, the solvent was removed under reduced pressure, and redissolved in an appropriate amount of dichloromethane, and then washed with water for 2 times, the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to obtain a crude product. The crude product obtained was separated by gel chromatography eluting with ethyl acetate to give 1- (2- (1H-imidazol-1-yl) ethyl) -1H-indole as a red oily liquid (yield 85%).
Step 5,1, 3, 5-tris (2-bromoethyl) -1,3, 5-triazacyclohexane-2, 4, 6-trione (0.6g,1.35mmol) and 1- (2- (1H-imidazol-1-yl) ethyl) -1H-indole (1.92g,8.07mmol) were added to a single-neck flask, 75ml of 1, 4-dioxane was added as a solvent, and heating was carried out to 105 ℃ with stirring and refluxing for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, the solvent is removed under reduced pressure, tetrahydrofuran is added to precipitate a large amount of solid, the solid is filtered, a filter cake is washed for 3 times by the tetrahydrofuran and dried to obtain a brown yellow solid 1,1' - ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tri (ethane-2, 1-diyl)) tri (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazole-3-onium) bromine salt (the yield is 78%).
Step 6, 1', 1 "- ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tris (ethane-2, 1-diyl)) tris (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazol-3-ium) bromide salt was dissolved in an appropriate amount of methanol. Under the condition of continuously stirring, slowly dropwise adding saturated ammonium hexafluorophosphate methanol solution until the precipitate is not separated out, and continuously stirring for 30 minutes. The filtrate was filtered, and the filter cake was washed 3 times with methanol and water, respectively, and dried to give 1,1', 1 "- ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tris (ethane-2, 1-diyl)) tris (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazol-3-ium) hexafluorophosphate as a yellow solid (yield 90%).
Step 7, [1,1 '-biphenyl ] -4,4' -disulfonic acid (300mg,0.954mmol) and potassium hydroxide (107.1mg,1.908mmol) were dissolved in 30ml of deionized water. The reaction solution was stirred at room temperature for 30 minutes, followed by vacuum freeze-drying to obtain white potassium [1,1 '-biphenyl ] -4,4' -disulfonate (yield 99%).
Step 8, 1', 1 "- ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tris (ethane-2, 1-diyl)) tris (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazol-3-ium) hexafluorophosphate (268.5mg,0.210mmol) and potassium [1,1' -biphenyl ] -4,4' -disulfonate (26.7mg,0.069mmol) were dissolved in 9.0ml of dimethyl sulfoxide solution and were sonicated for 3 minutes to facilitate complete dissolution. The pressure was reduced to-0.1 MPa, and the solvent was slowly removed at 90 ℃. And after the reaction is finished, cooling the obtained solid to room temperature to obtain the two-dimensional organic layer constructed based on the cation-pi interaction.
Example 6:
replacing steps 7 and 8 with steps 7a and 8 a:
step 7a, [1,1 '-biphenyl ] -4,4' -disulfonic acid (300mg,0.954mmol) and sodium hydroxide (71.2mg,1.908mmol) were dissolved in 30ml of deionized water. The reaction solution was stirred at room temperature for 30 minutes, followed by vacuum freeze-drying to give white sodium [1,1 '-biphenyl ] -4,4' -disulfonate (yield 99%).
Step 8a, 1', 1 "- ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tris (ethane-2, 1-diyl)) tris (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazol-3-ium) hexafluorophosphate (268.5mg,0.210mmol) and sodium [1,1' -biphenyl ] -4,4' -disulfonate (24.7mg,0.069mmol) were dissolved in 9.0ml of dimethyl sulfoxide solution and their complete dissolution was facilitated by sonication for 3 minutes. The pressure was reduced to-0.1 MPa, and the solvent was slowly removed at 90 ℃. And after the reaction is finished, cooling the obtained solid to room temperature to obtain another two-dimensional organic layer constructed based on cation-pi interaction.
Claims (7)
1. A preparation method for constructing a two-dimensional organic layer based on cation-pi interaction is characterized by comprising the following steps:
step 1: dissolving 1,3, 5-tri (2-hydroxyethyl) triazine-2, 4, 6-trione and triphenylphosphine in a molar ratio of 1: 3.6 in anhydrous acetonitrile, and cooling in an ice bath for 5-10 minutes; adding 3.6 equivalents of carbon tetrabromide under continuous stirring, recovering to room temperature during stirring, and reacting for 10-12 hours; removing solvent under reduced pressure, dissolving the concentrated solution in appropriate amount of dichloromethane, washing with saturated sodium chloride water solution for 1-2 times, mixing organic phases, drying with anhydrous sodium sulfate, and removing solvent under reduced pressure to obtain crude product;
separating the obtained crude product with gel chromatographic column, wherein the eluent is n-hexane to obtain white crystalline solid 1,3, 5-tris (2-bromoethyl) -1,3, 5-triazacyclohexane-2, 4, 6-trione;
step 2: sequentially mixing indole, 2-bromoethanol, tetrabutylammonium iodide and potassium hydroxide according to a molar ratio of 1: 2: 0.1: 3, and adding N, N-dimethylformamide as a solvent to obtain a solution; removing oxygen from the solution by a Schlenk technology, heating to 80-90 ℃ under the protection of nitrogen atmosphere, and stirring for reacting for 20-24 hours; after the reaction is finished, cooling the reaction mixture to room temperature, removing the solvent under reduced pressure, separating the residue by using a gel chromatographic column, and obtaining light yellow liquid 2- (1H-indol-1-yl) ethyl-1-ol by using petroleum ether and ethyl acetate as eluent, wherein the ratio of the petroleum ether to the ethyl acetate is 3: 1;
and step 3: mixing the 2- (1H-indol-1-yl) ethan-1-ol and triphenylphosphine in the step 2 according to a molar ratio of 1: 1.2, and adding 100ml of acetonitrile for ice bath cooling for 5-10 minutes; adding 1.2 equivalent carbon tetrabromide under continuous stirring, stirring and slowly returning to room temperature, and reacting for 5-6 hours; removing solvent under reduced pressure, dissolving the concentrated solution in 100ml dichloromethane, washing with saturated sodium chloride water solution for 2 times, mixing organic phases, drying with anhydrous sodium sulfate, and removing solvent under reduced pressure to obtain crude product; separating the obtained crude product with gel chromatographic column, wherein the eluent is n-hexane to obtain yellow oily liquid 2- (1H-indol-1-yl) ethyl-1-bromine;
and 4, step 4: dispersing sodium hydride in an anhydrous 1, 4-dioxane solution in a Schlenk flask, and then adding imidazole into the stirred mixed solution under the protection of nitrogen; then heating the mixture to 70-85 ℃, stirring and reacting for 1.0-1.5 hours; then dropwise adding the 2- (1H-indol-1-yl) ethyl-1-bromine obtained in the step (3) into the reaction solution, and after the system is stable, heating to 100-105 ℃ and refluxing for 10-12 hours; after the reaction is finished, cooling the reaction liquid to room temperature, removing the solvent under reduced pressure, dissolving the reaction liquid in 100ml of dichloromethane again, washing the reaction liquid for 2 times by using water, combining organic phases, drying the organic phases by using anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain a crude product; separating the obtained crude product with gel chromatographic column, wherein the eluent is ethyl acetate to obtain red oily liquid 1- (2- (1H-imidazole-1-yl) ethyl) -1H-indole;
and 5: mixing the 1,3, 5-tris (2-bromoethyl) -1,3, 5-triazacyclohexane-2, 4, 6-trione obtained in the step 1 and the 1- (2- (1H-imidazol-1-yl) ethyl) -1H-indole obtained in the step 4 according to a molar ratio of 1: 4.5, adding 1, 4-dioxane as a solvent, heating to 100-105 ℃, stirring and refluxing for 20-24 hours; after the reaction is finished, cooling to room temperature, decompressing to remove the solvent, adding tetrahydrofuran, precipitating a large amount of solid, filtering, washing a filter cake for 3-4 times by using tetrahydrofuran, and drying to obtain a brown yellow solid 1,1' - ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tri (ethane-2, 1-diyl)) tri (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazole-3-onium) bromine salt;
step 6: dissolving the 1,1' - ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tri (ethane-2, 1-diyl)) tri (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazole-3-onium) bromine salt obtained in the step 5 in 50-70 mL of methanol; dropwise adding a saturated ammonium hexafluorophosphate methanol solution under stirring until the precipitate is not separated out, and continuously stirring for 30-40 minutes; filtering, washing a filter cake with methanol and water for 3-4 times respectively, and drying to obtain a yellow solid 1,1' - ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tri (ethane-2, 1-diyl)) tri (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazole-3-onium) hexafluorophosphate;
and 7: dissolving [1,1 '-biphenyl ] -4,4' -disulfonic acid and potassium hydroxide in deionized water according to a molar ratio of 1: 2, stirring the reaction solution at room temperature for 15-30 minutes, and then carrying out vacuum freeze drying to obtain white potassium [1,1 '-biphenyl ] -4,4' -disulfonate;
and 8: dissolving 1,1' - ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tri (ethane-2, 1-diyl)) tri (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazole-3-onium) hexafluorophosphate obtained in the step 6 and potassium [1,1' -biphenyl ] -4,4' -disulfonate obtained in the step 7 in a dimethyl sulfoxide solution according to a molar ratio of 3: 1, and performing ultrasonic treatment for 3 minutes to promote complete dissolution; reducing the pressure to-0.09 to-0.1 MPa, and completely removing the solvent at 90 to 95 ℃; and after the reaction is finished, cooling the obtained solid to room temperature to obtain the two-dimensional organic layer constructed based on the cation-pi interaction.
2. The method of claim 1, wherein the method comprises: replacing step 7 and step 8 with the following step 7a and step 8a, another two-dimensional organic layer built on the basis of cation-pi interactions was obtained:
step 7 a: dissolving [1,1 '-biphenyl ] -4,4' -disulfonic acid and sodium hydroxide in deionized water according to a molar ratio of 1: 2, stirring for 15-30 minutes at room temperature, and then carrying out vacuum freeze drying to obtain white [1,1 '-biphenyl ] -4,4' -disulfonic acid sodium;
step 8 a: dissolving 1,1' - ((2,4, 6-trioxo-1, 3, 5-triazine-1, 3, 5-triyl) tri (ethane-2, 1-diyl)) tri (1- (2- (1H-indol-1-yl) ethyl) -1H-imidazole-3-onium) hexafluorophosphate obtained in the step 6 and [1,1' -biphenyl ] -4,4' -disulfonic acid sodium obtained in the step 7a in dimethyl sulfoxide solution according to a molar ratio of 3: 1, and performing ultrasonic treatment for 2-3 minutes to promote complete dissolution; reducing the pressure to-0.09 to-0.1 MPa, and completely removing the solvent at 90 to 95 ℃; and after the reaction is finished, cooling the obtained solid to room temperature to obtain another two-dimensional organic layer constructed based on cation-pi interaction.
3. The method of claim 1 or 2, wherein the method comprises the following steps: the Schlenk technique is as follows: after the reactants and the solvent were added to a dried Schlenk tube, the tube was frozen with liquid nitrogen, and then, under the atmosphere of nitrogen, vacuum was applied, nitrogen was introduced, and then, liquid nitrogen was again frozen, and thus, the freezing-thawing-freezing operation was repeated several times.
4. The method of claim 1 or 2, wherein the method comprises the following steps: the anhydrous acetonitrile is a solvent obtained after drying a 5A molecular sieve.
5. The method of claim 1 or 2, wherein the method comprises the following steps: the 1, 4-dioxane solvent is a solvent obtained by drying a 5A molecular sieve.
6. The method of claim 1 or 2, wherein the method comprises the following steps: all solution heating was carried out under constant temperature oil bath conditions.
7. The method of claim 1 or 2, wherein the method comprises the following steps: the solution is cooled in an ice bath at the temperature of 0 ℃ in an ice-water mixture.
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